Issue 13, 1975

Activation of copper(II) ammine complexes by molecular oxygen for the oxidation of thiosulphate ions

Abstract

The stoicheiometry and kinetics of reaction of aqueous-ammonia (0·1–1.0M) solutions of copper(II) ions with thiosulphate ion in the presence of oxygen have been examined. The amount of oxygen consumption and the relative amounts of the final sulphur products, namely trithionate and sulphate ions, are dependent on the initial [S2O3]2– concentration and pH. The detailed kinetics of the reaction at pH 11·2 suggest mechanisms in which O2 becomes axially associated with amminethiosulphatocopper(II) species. In this role O2 assists in electron transfer between [S2O3]2– and CuII. The most active species for [S3O6]2– formation is a tetra-amminecopper(II) complex having one axial [S2O3]2– and one axial O2 ligand. A triamminecopper(II) complex, having both axial and equatorial [S2O3]2– ligands as well as an axial O2, is suggested as the reactive intermediate for [SO4]2–formation. The role of the intermediate CuII species is one of complexing both oxidant and reductant.,in that it provides a mechanism for electron transfer and allows O2 to interact via an ionic mechanism.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1975, 1329-1338

Activation of copper(II) ammine complexes by molecular oxygen for the oxidation of thiosulphate ions

J. J. Byerley, S. A. Fouda and G. L. Rempel, J. Chem. Soc., Dalton Trans., 1975, 1329 DOI: 10.1039/DT9750001329

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements